CN100430316C - Preparation method of molecular engram silicon oxide nanometer particle with sensing molecule identification to TNT - Google Patents
Preparation method of molecular engram silicon oxide nanometer particle with sensing molecule identification to TNT Download PDFInfo
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- CN100430316C CN100430316C CNB2006101560523A CN200610156052A CN100430316C CN 100430316 C CN100430316 C CN 100430316C CN B2006101560523 A CNB2006101560523 A CN B2006101560523A CN 200610156052 A CN200610156052 A CN 200610156052A CN 100430316 C CN100430316 C CN 100430316C
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Abstract
This invention relates to a chemical preparation method of molecular imprinting silicon oxide nanometer particle that possesses sensitive molecular recognition for TNT. It includes: use silicon oxide globular particle as template, modify ammonia propyl on its surface, amidate silicon oxide globular particle, and make its surface taking specified functional group. Preparation of this invention includes following two steps: low-grade polymerize reacting metamer at invariable reaction condition, form oligomer, form coating on template surface, change reaction condition, polymerize coating of template surface, form cross linking outer shell. Ripen coating of globular template surface in cross linking polymerization process, form high cross linking polymer nanometer outer shell, make nanometer outer shell with strong rigidity, large specific surface area, stable spatial structure of forming site, many sites, and good selectivity, and form controllable thick shell nucleocapsid nanometer compound ball taking molecular recognition function.
Description
Affiliated field the present invention relates to material science, particularly has the chemical preparation process that TNT is had the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification.
Background technology
Silicon oxide mixture nanometer ball all has in a lot of fields widely and uses with its superior characteristic.As in medical science and field of biology: silicon oxide mixture nanometer ball can be used as drug delivery system, cushion effectively is sent to lesions position or realizes that controlled delivery of pharmaceutical agents discharges; Silicon oxide mixture nanometer ball can also be used for biomacromolecule, as diagnosis of micro encapsulation, migration and release, gene therapy and the disease of protein, enzyme and nucleic acid etc.At material science:, can effectively improve the intensity and the hardness of matrix material as the filler of polymer composites because the core of mixture nanometer ball is the monox nanometer particle; Silicon oxide mixture nanometer ball can be given the coating opacity as the filler of coating; When using, can also improve the gloss of papery, perhaps be used for rubber toughened plastics technology as papermaking material.Catalyst field: silicon oxide mixture nanometer ball can be used for the protection of hydridization type Preparation of catalysts and photosensitive component.Silicon oxide mixture nanometer ball also can be used as microreactor and uses, the preparation inorganic nanoparticles.In addition, silicon oxide mixture nanometer ball also can be used as UV light absorber, is used for cosmetic industry protection skin and hair and is not subjected to uv-radiation.
Therefore, the preparation of silicon oxide mixture nanometer ball always is one of research focus of polymer science.The method for preparing silicon oxide mixture nanometer ball that present people have been developed mainly contains following three kinds: self-assembly method, template and microemulsion-dispersion copolymerization method.Wherein template is the simplest method for preparing the mixture nanometer ball, adopt this method can obtain uniform single dispersed complex nanometer ball easily, and can obtain being fit to the mixture nanometer ball of demand further by the particle diameter of control nuclear template and size and the thickness of the shell that follow-up monomeric consumption is adjusted nuclear.Utilize template to prepare the mixture nanometer ball and have two types: the first allows the polyelectrolyte that has opposite charges in the self-assembly successively of spherical template surface, reach the shell that needs thick after; Another kind of template is at template surface chemical bonding polymerizable or crosslinkable molecular layer, initiated polymerization or crosslinked.In order to obtain Hollow Compound thing nanometer ball, it is necessary utilizing suitable removal of solvents template simultaneously.Conventional method is by hydrofluoric acid and acetone mixing solutions or Neutral ammonium fluoride and acetone mixing solutions and silicon oxide nuclear reaction, micropore on the shell diffuses out reacted nuclear consitution, these micropores generally very little (＜10nm), reacted product diffuses out, thereby forms hollow polymer nanocomposite shell.
The application facet of mixture nanometer ball, also having is the thickness that utilizes exine shells greatly.Shell is thick too thick, and is bigger to the influence of the recognition performance of mixture nanometer ball.Controlled shell is thick has the substitute that the molecular imprinting monox nanometer complex particle that TNT is had sensitive molecule identification can be used as the carrier of molecular recognition, shows better practicality and more wide application prospect.Research about this respect is at the early-stage, and slower development, still is in phenomenon and describes the stage.Can pass through as the template for preparing molecularly imprinted polymer such as report in the article of Klaus Mosbach scientific research group on 2002 " Journal of Materials Chemistry " at porous silica; Report is by the synthetic single dispersing molecule imprinted polymer microballoon of precipitation polymerization in the article of Peter A.G.Cormack scientific research group on 2003 " Angew.Chem.Int.Ed. ".
The method that is reported in initiator in the finishing of how empty silicon oxide in the article of Sellergren scientific research group on 2006 " Chem.Mater. " has been synthesized core-shell type molecularly imprinted polymer microballoon.
Because above-mentioned preparation method's restriction, molecularly imprinted polymer all is the marking on micron-sized template, and selectivity and monodispersity are all poor, and
It is the dispersed relatively poor of unsettled molecular imprinting composite ball that initiator is modified at how empty silicon oxide surface by Sellergren scientific research group, recognition performance is lower, the thickness of shell is uncontrollable, and all is that other molecule is had recognition function, rather than to the TNT molecular recognition.But the preparation method who has the thick mixture nanometer ball of the controlled shell of TNT molecular recognition who therefore develops a kind of functionalization has great importance.
In recent decades, in order to improve marking ability, the morphology control of molecularly imprinted polymer has been attracted large quantities of investigators.2005
The patent of invention of Sellergren scientific research group (US, PAT.NO.6,881,804) discloses " Porous, molecularly imprinted polymer and a process for thepreparation thereof " preparation method.It has adopted following step: empty silicon oxide outside, (1) non-hole coats one deck porous air silicon oxide as ball type carrier, median size 2-10um; (2) function monomer methyl methacrylate (MMA) and target molecule 9-(2-aminoethyl) VITAMIN B4 are distributed in the solvent, and then are diffused in the duct of porous silica; (3), stir with linking agent ethyleneglycol dimethacrylate methyl esters (EGDMA), initiator Diisopropyl azodicarboxylate (AIBN) and solvent; (4) above-mentioned solution is mixed, seal behind the feeding nitrogen, promptly get molecularly imprinted polymer 60 ℃ of isothermal reactions.But because effectively the molecular imprinting site mainly is present on surface or the very shallow one deck shell, the polymkeric substance of the marking in how empty silicon oxide duct wherein has a lot of markings site to be positioned at the inside of polymkeric substance, just can cause the waste of marking point largely.As further development, people utilize template to synthesize large quantities of nucleocapsid structure composite ball with marking shell.Yet, as the extension of nucleocapsid structure ball and in theory the mixture silicon oxide nanoparticle molecular recognition of marking better effects if be not in the news as yet.Because the density of imprinted polymer is more taller than general cross-linked polymer, the site of a large amount of molecularly imprinted polymers all is to be positioned at outer surface layer, and the specific surface area of nanometer layer is big thereby recognition site is many, and selectivity is good.
Summary of the invention
Goal of the invention: at the weak point of present prior art existence, the present invention utilize first nano silicon oxide as template synthesized have controlled shell thick TNT is had the chemical preparation process of the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification, and first nano silicon oxide composite ball functionalization is used for molecular imprinting.Described method is a chemical synthesis, and at first Zhi Bei monodisperse sol monox nanometer granular core structure is carried out two step finishinges, and then carries out two step chemical reactions in its surface coating, makes its functionalization.
Technical scheme of the present invention is: a kind of chemical preparation process that TNT is had the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification comprises with the spherical particle of silicon oxide and makes template that aminopropyl in its finishing is characterized in that; The further amidation again of the spherical particle of described silicon oxide makes its surface with specific functional group, and preparation process of the present invention comprises following two steps:
1.1 with function monomer, be identified in the acetonitrile that molecule and linking agent be dissolved in 50 milliliters and make its concentration be respectively 0.0020～0.0046 mol, 0.00264 mol and 0.0080～0.0184 mol, add massfraction again and be the spherical template that 2～5% initiator and 20 milligram of two step modify, seal behind the logical nitrogen deoxidation, be warming up to 50 ℃ of reactions 6 hours, form oligomer on the spherical template surface, and then being warming up to 60 ℃ of reactions formed polymkeric substance in 18 hours on the spherical template surface coating layer, it is the first step reaction;
1.2 the reaction of second step is that reaction system is warmed up to 85 ℃ of reactions 8 hours again, the further slaking of the coating layer on spherical template surface in the crosslinking polymerization process, formed highly cross-linked polymer shell, make the rigidity of shell of polymkeric substance strong, space structure in the formation site is stable, selectivity is good, forms to have the thick nuclear shell structure nano composite ball of the controlled shell of molecular recognition performance;
Be distributed in ethanolic soln, the deionized water more respectively with gained nuclear shell structure nano composite ball is centrifugal, remove not complete reaction thing ultrasonic centrifugal three times, be to extract in ethanol/acetic acid solution of 8: 2 to be identified molecule again with the volume ratio that is dispersed in 50mL of nano-complex ball, be identified molecule and diffuse out by the perforate on the shell and be dissolved in the solution, wash the nano-complex ball that just obtains having molecular recognition function for three times again.
As a further improvement of existing technologies, the thickness of the shell of the nuclear shell structure nano composite ball that said controlled shell is thick can be controlled by proportioning and the total amount adjusted between the follow-up monomer; Said spherical template is modified the silicon oxide bead that is rich in acrylamide for the surface through two steps; The said molecule that is identified is TNT; Said function monomer is functional monoene class monomer: acrylamide (AAM); Said linking agent is a polyenoid class monomer ethyleneglycol dimethacrylate methyl esters (EGDMA); Said initiator is oil-soluble initiator azo-bis-isobutyl cyanide (AIBN).
Beneficial effect with respect to prior art:
One: with respect to prior art, 2005
The patent of invention of Sellergren scientific research group (US, PAT.NO.6,881,804) discloses " Porous, molecularly imprinted polymer and aprocess for the preparation thereof " preparation method.It has adopted median size is that the empty silicon oxide outside, non-hole of 2-10um coats one deck porous air silicon oxide as spherical template, be distributed in the solvent, form mixed solution, again with function monomer methyl methacrylate (MMA), linking agent ethyleneglycol dimethacrylate methyl esters (EGDMA), being identified molecule 9-(2-aminoethyl) VITAMIN B4 and initiator Diisopropyl azodicarboxylate (AIBN) mixes with above-mentioned solution, be diffused into then in the duct of porous silica, seal after feeding nitrogen again, promptly get molecularly imprinted polymer 60 ℃ of isothermal reactions.But because effectively the molecular imprinting site mainly is present on surface or the very shallow one deck shell, the polymkeric substance of the marking in the porous silica duct wherein has a lot of markings site to be positioned at the inside of polymkeric substance, just can cause the waste of marking point largely.
It is that the spherical particle of non-hole silicon oxide of 100nm is made template that the present invention has adopted median size, aminopropyl in its finishing, the further amidation again of the spherical particle of silicon oxide after the modification, make its surface with specific functional group, preparation process of the present invention comprises two steps: at first the spherical particle template of the silicon oxide that 20 milligram of two step modified is distributed in the acetonitrile, with function monomer third rare acid amides (AAM), linking agent ethyleneglycol dimethacrylate methyl esters (EGDMA), being identified molecule TNT mixes with above-mentioned solution, add massfraction again and be 2～5% initiator, seal behind the logical nitrogen deoxidation, be warming up to 50 ℃ of reactions 6 hours, form oligomer on the spherical template surface, and then be warming up to 60 ℃ of reactions formed polymkeric substance in 18 hours on the spherical template surface coating layer, it is the first step reaction.The reaction of second step is that reaction system is warmed up to 85 ℃ of reactions 8 hours again, the further slaking of the coating layer on spherical template surface in the crosslinking polymerization process, formed highly cross-linked polymer shell, make the rigidity of shell of polymkeric substance strong, space structure in the formation site is stable, selectivity is good, forms to have the thick nuclear shell structure nano composite ball of the controlled shell of molecular recognition performance.
In sum, nano molecular marking technology especially coats one deck as template by precipitation polymerization at nano silicon oxide bead nuclear and has the nanoshell of recognition performance, thereby increase the specific surface area of nanometer polymer layer, increased the molecular recognition site, improve selectivity, binding capacity and identity.
Its two: in the method provided by the present invention, the thickness of the shell of the nuclear shell structure nano composite ball that controlled shell is thick can be controlled by proportioning and the total amount adjusted between the follow-up monomer.The thickness that promptly has the recognition performance shell can be controlled, therefore, and can be by optimizing the nano-complex ball that reaction conditions obtains being fit to needs.Another big advantage of method provided by the present invention is can add to be identified the nano-complex ball that molecule TNT obtains having certain specific function.Can anamorphic zone marking nano-complex ball such as adding a certain amount of TNT, simultaneously also can be with amino acid as the molecule that is identified, as tryptophane.And the function monomer among the present invention is acrylamide (AAM).As seen, method provided by the present invention is general, and usage range is more extensive.
Its three: compare with traditional molecularly imprinted polymer, the nano molecular imprinted polymer has bigger specific surface area, more recognition site, bigger binding capacity and quick binding kinetics improve molecular recognition performance and selectivity.Illustrated among Fig. 7 that institute's synthetic has the molecular imprinting characteristic of the nano-complex ball of TNT marking point.The saturated absorption curve that two kinds of molecule marking materials are arranged among Fig. 7 A: (a) be the nano-complex ball; (b) be traditional polymer microballoon.By Fig. 7 A as can be known, the nano-complex ball has higher saturated extent of adsorption, is 3 times of traditional molecularly imprinted polymer microballoon; The kinetic curve that two kinds of molecule marking materials are arranged among Fig. 7 B: (a) be the nano-complex ball; (b) be traditional polymer microballoon.By among Fig. 7 B as can be known, the nano-complex ball has association rate faster, is 3 times of traditional molecularly imprinted polymer ball.
Its four: select colloidal sol monox nanometer particle as the spherical template purpose because it has the following advantages:
(1) synthetic easily colloidal sol monox nanometer particle, its particle size range can be from 5nm-2000nm, bigger surface-area, relatively low cost; (2) stability that has chemistry and heat in reaction process is not reacted with organic solvent; (3) the easy grafting organo-functional group in surface; (4) environmental sound.
Description of drawings
Fig. 1 is the formation mechanism synoptic diagram of gained nano-complex ball of the present invention.
Fig. 2 is the sem photograph that the silicon oxide bead of acrylamide is rich on surface of the present invention.
Fig. 3 is the resulting intermediate product of the present invention---the infrared spectrum of the silicon oxide that two steps modified.
Fig. 4 is nuclear-shell transmission electron microscope picture that the present invention has recognition performance.
Fig. 5 is the nano-complex ball transmission electron microscope picture that the present invention has recognition performance.
Fig. 6 is the thick nano-complex ball transmission electron microscope picture of controlled shell that the present invention has recognition performance.
Fig. 7 is the saturated binding capacity curve and the kinetic curve figure of synthetic nano-complex ball of the present invention.
Further explain embodiment with reference to the accompanying drawings
Fig. 1 is the formation mechanism synoptic diagram of gained nano-complex ball of the present invention.In Fig. 1, successively the silica sol nano grain surface is carried out amination and amidation two steps modification, utilize the silicon oxide spheres as template of two steps modification, adopt two step chemical reactions, obtained the nano-complex ball.
The silica sol particle must be modified, and makes the surface be with extraordinary functional group, is beneficial to silicon oxide nanoparticle and is dispersed in organic solvent easily next step is reflected at its surface and takes place when neutralization.What the present invention adopted is in pure silica sol particle surface graft aminopropyl and acrylate chloride reaction, make its surface coverage acrylamide, help like this add function monomer and promptly have amino acrylamide and be adsorbed on the silica sol particle surface, make to be reflected at its surface and to take place;
Two step chemical reactions are meant and at first allow reaction soln be in lesser temps, carry out slight polymerization in reasonable time, form oligomer, form an integument on the silicon oxide ball surface of modifying, and the thickness of this skim is most important, needs carefully control.Be warmed up to comparatively high temps then, the further polymerization of the adsorption layer on silicon oxide ball surface.In reaction thereafter, remain in function monomer in the solution and be adsorbed on again and carry out polymerization on the shell, therefore can adjust the thickness of gained spherical shell by the monomeric consumption of controlled function.Further heating up makes oligomer and the further polymerization of function monomer in the shell, and this process is referred to as slaking, and purpose makes its rigidity stronger.
Fig. 2 is the sem photograph that the silicon oxide bead of acrylamide is rich on surface of the present invention, owing to adopt two step modifying method, at pure silica bead surface graft aminopropyl and and then obtain the electron scanning micrograph that the monox nanometer ball of acrylamide is rich on the surface with the acrylate chloride reaction.
Fig. 3 is the resulting intermediate product of the present invention---the infrared spectrum of the silicon oxide that two steps modified.Can clearly find out that from infrared spectrum modifying two peak positions that go up aminopropyl is respectively 1400cm
-1And 1450cm
-1, the amide group peak position is at 1725cm
-1The peak position value of this infrared spectrum shows to modify and has gone up acrylamide.
Fig. 4 is nuclear-shell transmission electron microscope picture that the present invention has recognition performance: (A) polymer shell of the marking on the 100nm monox nanometer ball is resultant product---the nano-complex ball of nucleocapsid structure that gets of the present invention.Can coat one deck nanoshell on the spherical template surface through two-step reaction method.Can clearly see nucleocapsid structure on the scanned photograph, as seen, the nuclear shell structure nano composite ball is made up of two portions: intermediary spherical template and very thin nanometer shell.
Fig. 5 is the nano-complex ball transmission electron microscope picture that the present invention has recognition performance: (A) polymer shell of the marking on the 100nm monox nanometer ball, shell is thick to be approximately about 30nm.Illustration on Fig. 5 is the transmission photo of the nano-complex ball of amplification, and its shape characteristic is high-visible.
Fig. 6 is the thick nano-complex ball transmission electron microscope picture of controlled shell that the present invention has recognition performance.At particle diameter is that the silicon oxide surface preparation that 100nm modifies has the thick controlled core-shell type molecularly imprinted polymer of recognition performance shell: (A) the thick 30nm of being approximately of the shell of polymkeric substance.
Fig. 7 is the saturated binding capacity curve and the kinetic curve figure of synthetic nano-complex ball of the present invention.
Wherein Fig. 7 A is the saturated absorption curve of two kinds of molecule marking materials: (a) be the nano-complex ball; (b) be traditional polymer microballoon.As seen, having the nano-complex ball has higher saturated extent of adsorption, is 3 times of traditional polymer microballoon.Fig. 7 B is the curve of adsorption kinetics of nano-complex ball (a) and traditional polymer microballoon (b), and the former has association rate faster, is more than 3 times of the latter.
Embodiment:
A kind of chemical preparation process that TNT is had the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification comprises with the spherical particle of silicon oxide and makes template that aminopropyl in its finishing is characterized in that; The further amidation again of the spherical particle of described silicon oxide makes its surface with specific functional group, and preparation process of the present invention comprises following two steps:
The first step, function monomer, be identified in the acetonitrile that molecule and linking agent be dissolved in 50 milliliters and make its concentration be respectively 0.0020～0.0046 mol, 0.00264 mol and 0.0080～0.0184 mol, add massfraction again and be the spherical template that 2～5% initiator and 20 milligram of two step modify, seal behind the logical nitrogen deoxidation, be warming up to 50 ℃ of reactions 6 hours, form oligomer on the spherical template surface, and then be warming up to 60 ℃ of reactions 18 hours and form low polymeric coating layer on spherical template surface, it reacts for the first step;
Second step, reaction system is warmed up to 85 ℃ of reactions 8 hours again, the further slaking of the coating layer on spherical template surface has formed highly cross-linked polymer shell in the crosslinking polymerization process, makes the rigidity of shell of polymkeric substance stronger.Space structure in the site that forms is more stable, and selectivity is stronger.
If the amount of the silicon oxide ball of keep modifying is constant, change the reaction monomers total amount, the total amount of function monomer and linking agent is doubled, just can change the thickness of shell, shell is thick changes into 10nm from 30nm, as shown in Figure 6.
Reaction monomers can add and is identified molecule, changes the performance of shell.As adding an amount of TNT, the imprinted polymer that the rigidity that not only can improve shell can also form TNT carries out molecular recognition.
Embodiment: according to the precipitation polymerization reaction, utilize nano silicon oxide to make template, adopt two-step reaction can obtain the nano-complex ball.
1, the single dispersion synthesizing of silica sol nanometer ball: at room temperature, 3.6ml tetraethoxy (TEOS) is dissolved in the ethanol of 88.1ml and stirred three minutes, 11.9ml ammoniacal liquor (25%) is added in the above-mentioned reaction mixture rapidly, violent stirring three minutes, and Wen He stirring is 24 hours then.Gained silica sol nanometer ball is distributed in the toluene through three centrifuge washings.
(1) the monox nanometer particles dispersed of above-mentioned gained drips the aminopropyl triethoxysilane (APTS) of 1ml then in the toluene of 50ml, refluxes 24 hours under inert atmosphere.Being distributed in the toluene of the product of gained through three centrifuge washings.
(2) in the monox nanometer particle solution of above-mentioned modification, add the Anhydrous potassium carbonate of 0.2g, 5 of ultra-sonic dispersion minutes then, the acrylate chloride that drips 1ml again is stirring reaction 12 hours at room temperature.The resulting polymers microballoon is distributed in the acetonitrile through three centrifuge washings.
2, function monomer, being identified in the acetonitrile that molecule and linking agent be dissolved in 50 milliliters makes its concentration be respectively 0.0020～0.0046 mol, 0.00264 mol and 0.0080～0.0184 mol, add massfraction again and be the spherical template of silicon oxide that 2～5% initiator and 20 milligram of two step modify, seal behind the logical nitrogen deoxidation, be warming up to 50 ℃ of reactions 6 hours, form oligomer on the spherical template surface, and then be warming up to 60 ℃ of reactions 18 hours and form low polymeric coating layer on spherical template surface, thereby formed the nuclear shell structure nano composite ball.
Claims (2)
1, a kind of chemical preparation process that TNT is had the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification, comprise with the spherical particle of nano silicon oxide and make template, aminopropyl in its finishing, it is characterized in that: the further amidation again of the spherical particle of described nano silicon oxide, obtain the nano silicon oxide particle that the surface has acrylamide functional group, the preparation process of present method comprises following two steps:
1.1 with acrylamide, being identified in the acetonitrile that molecule TNT and linking agent polyenoid class monomer ethyleneglycol dimethacrylate methyl esters be dissolved in 50 milliliters makes its concentration be respectively 0.0020～0.0046 mol, 0.00264 mol and 0.0080～0.0184 mol, add massfraction again and be 2～5% initiator azo-bis-isobutyl cyanide and 20 milligrams of surfaces and have the nano silicon oxide particle of acrylamide functional group, seal behind the logical nitrogen deoxidation, be warming up to 50 ℃ of reactions 6 hours, form oligomer at the nano silicon oxide particle surface that has acrylamide functional group, and then being warming up to 18 hours coating layers of 60 ℃ of reactions at the nano silicon oxide particle surface formation polymkeric substance that has acrylamide functional group, it is the first step reaction;
1.2 the reaction of second step is that reaction system is warmed up to 85 ℃ of reactions 8 hours again, in the crosslinking polymerization process, have the further slaking of coating layer of the nano silicon oxide particle surface of acrylamide functional group, formed highly cross-linked polymer shell, make the rigidity of shell of polymkeric substance strong, space structure in the formation site is stable, selectivity is good, forms to have the thick nuclear shell structure nano composite ball of the controlled shell of molecular recognition performance;
Be distributed in ethanolic soln, the deionized water more respectively with gained nuclear shell structure nano composite ball is centrifugal, remove not complete reaction thing ultrasonic centrifugal three times, the volume ratio that again the nano-complex ball is dispersed in 50mL is to extract in ethanol/acetic acid solution of 8: 2 to be identified molecule TNT, be identified molecule TNT and diffuse out by the perforate on the shell and be dissolved in the solution, wash the nano-complex ball that just obtains having molecular recognition function for three times again.
2, according to claim 1 a kind ofly have the chemical preparation process of the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification to TNT, and it is characterized in that: the thickness of the shell of the nuclear shell structure nano composite ball that said controlled shell is thick can be controlled by proportioning and the total amount adjusted between the follow-up function monomer acrylamide.
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| CN101845127B (en) * | 2010-05-10 | 2011-09-21 | 南京医科大学 | Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound |
| CN102253201A (en) * | 2011-05-04 | 2011-11-23 | 皖西学院 | Research on chemiluminescent immunosensor based on surface imprinted hollow particles |
| CN103086812B (en) * | 2013-02-04 | 2015-01-07 | 中国工程物理研究院化工材料研究所 | Preparation method of bicomponent energetic material core-shell structure |
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